US2024425396A1PendingUtilityA1

Method and system for the remediation of aquatic facilities

Assignee: TRUOX INCPriority: Mar 18, 2021Filed: Aug 28, 2024Published: Dec 26, 2024
Est. expiryMar 18, 2041(~14.7 yrs left)· nominal 20-yr term from priority
Inventors:Roy W. Martin
C02F 1/66C02F 2303/04C02F 2209/006C02F 2209/06C02F 1/008C02F 2209/29C02F 2103/42C02F 1/76C01B 11/024
70
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Claims

Abstract

A system and method for controlling multiple methods of remediation cycles for the treatment of water of an aquatic facility for immersion by humans using a process controller programmed to obtain a targeted chlorine dioxide CT Value in the water. The system controls remediation cycles having different completion time intervals and chlorine dioxide setpoints using integrated chemical feed systems.

Claims

exact text as granted — not AI-modified
1 . An integrated system for controlling multiple methods of remediation cycles for the treatment of water of an aquatic facility for immersion by humans, the integrated system comprising:
 a chlorine dioxide sensor in fluid communication with the water;   a chlorine dioxide feed system in fluid communication with the water, the chlorine dioxide feed system is downstream of the chlorine dioxide sensor, and chlorine dioxide is fed to the water during ON-Time;   a process controller in communication with the chlorine dioxide sensor and the chlorine dioxide feed system for measurement and control of chlorine dioxide in the water;   the process controller is programmed to control recovery remediation cycles and routine remediation cycles of the water, the recover remediation cycles having a different completion time interval and ClO 2  Setpoint than the routine remediation cycles, and completion of the recovery remediation cycles and the routine remediation cycles is determined by achieving a targeted chlorine dioxide CT Value in the water;   the process controller is programmed to control the chlorine dioxide feed system using remedial time-based proportional control (remedial TBP), wherein the remedial TBP determines the chlorine dioxide feed system ON-Time following the formula:   
       
         
           
             
               
                 
                   [ 
                   
                     
                       
                         
                           ClO 
                           2 
                         
                         ⁢ 
                             
                         Setpoint 
                         ⁢ 
                             
                         
                           ( 
                           ppm 
                           ) 
                         
                       
                       - 
                       
                         Measured 
                         ⁢ 
                             
                         
                           ClO 
                           2 
                         
                         ⁢ 
                             
                         
                           ( 
                           ppm 
                           ) 
                         
                       
                     
                     
                       
                         ClO 
                         2 
                       
                       ⁢ 
                           
                       Dynamic 
                          
                       × 
                          
                       10 
                          
                       × 
                          
                       Dynamic 
                       ⁢ 
                           
                       Compensation 
                     
                   
                   ] 
                 
                    
                 × 
                    
                 Time 
                 ⁢ 
                     
                 Segment 
               
               = 
               
                 ON 
                 - 
                 Time 
               
             
           
         
       
       where,
 Time Segment is a segment of time reported in seconds or minutes; 
 ClO 2  Setpoint (ppm) is the ClO 2  Setpoint for the selected routine remediation cycle or recovery remediation cycle; 
 Measured ClO 2  (ppm) is the ClO 2  value measured by a chlorine dioxide sensor; 
 ClO 2  Dynamic is a concentration of ClO 2  being fed to the water from the chlorine dioxide feed system and is based on a total volume of water being treated per unit time (ClO 2  ppm/minute); and 
 Dynamic Compensation (DC) is a unique value for each aquatic facility and compensates effects of lag-time on measurement of the chlorine dioxide concentration in the water by the chlorine dioxide sensor after chlorine dioxide has been fed to the water from the chlorine dioxide feed system, and the DC has a value ranging from 0.2 to 2.0. 
 
     
     
         2 . The system in accordance with  claim 1 , wherein the Dynamic Compensation value is 1.0. 
     
     
         3 . The system in accordance with  claim 1 , further comprising optimizing the Dynamic Compensation following the formula: 
       
         
           
             
               
                 DC 
                 ⁢ 
                     
                 
                   ( 
                   
                     Optimized 
                     ⁢ 
                         
                     Value 
                   
                   ) 
                 
               
               = 
               
                 Theoretical 
                 ⁢ 
                     
                 
                   ClO 
                   2 
                 
                 ⁢ 
                     
                 
                   ( 
                   ppm 
                   ) 
                 
                 ⁢ 
                     
                 increase 
                 / 
                 Deviation 
                 ⁢ 
                     
                 from 
                 ⁢ 
                     
                 Setpoint 
                 ⁢ 
                     
                 
                   ( 
                   ppm 
                   ) 
                 
                    
                 × 
                    
                 Y 
               
             
           
         
       
       Where, 
       
         
           
             
               
                 “ 
                 
                   Theoretical 
                   ⁢ 
                       
                   
                     ClO 
                     2 
                   
                   ⁢ 
                       
                   
                     ( 
                     ppm 
                     ) 
                   
                   ⁢ 
                       
                   increase 
                 
                 ” 
               
               = 
               
                 
                   ( 
                   
                     ON 
                     - 
                     Time 
                     / 
                     Time 
                     ⁢ 
                         
                     segment 
                   
                   ) 
                 
                    
                 × 
                    
                 lag 
                 - 
                 time 
                    
                 × 
                    
                 
                   ClO 
                   2 
                 
               
             
           
         
       
       Dynamic
 “Deviation from Setpoint”=ClO 2  Setpoint-Measured ClO 2    
 “Y” is the “Lag-time Adjustment” having a value ranging from 1.01 to 2.0, preferably 1.05 to 1.8, and most preferred 1.1 to 1.5. 
 
     
     
         4 . The system in accordance with  claim 3 , wherein the Dynamic Compensation is automatically optimized by the process controller. 
     
     
         5 . The system in accordance with  claim 3 , wherein the Dynamic Compensation is optimized manually. 
     
     
         6 . The system in accordance with  claim 1 , wherein the Recovery Remediation cycle having a completion time interval ranging between 0.25 to 3.5 hours and a ClO 2  Setpoint ranging from 2 to 20 ppm. 
     
     
         7 . The system in accordance with  claim 6 , wherein the ClO 2  Setpoint ranges from 3 to 15 ppm. 
     
     
         8 . The system in accordance with  claim 7 , wherein the ClO 2  Setpoint ranges from 4 to 10 ppm. 
     
     
         9 . The system in accordance with  claim 1 , wherein the Routine Remediation cycle having a completion time interval ranging between 3.5 to 24 hours and a ClO 2  Setpoint ranging from 0.2 to 1.0 ppm. 
     
     
         10 . The system in accordance with  claim 9 , wherein the ClO 2  Setpoint ranges from 0.2 to 0.8 ppm. 
     
     
         11 . The system in accordance with  claim 10 , wherein the ClO 2  Setpoint ranges from 0.3 to 0.6 ppm. 
     
     
         12 . The system in accordance with  claim 6 , wherein the Recovery Remediation further comprises a Biofilm Remediation cycle and a Shock Remediation cycle. 
     
     
         13 . The system in accordance with  claim 12 , wherein the Bio-film Remediation cycle having a chlorine dioxide CT Value ranges from 300 to 3000 (mg/l×min). 
     
     
         14 . The system in accordance with  claim 13 , wherein the chlorine dioxide CT Value ranges from 400 to 2500 (mg/l×min). 
     
     
         15 . The system in accordance with  claim 14 , wherein the chlorine dioxide CT Value ranges from 500 to 2000 (mg/l/min). 
     
     
         16 . The system in accordance with  claim 12 , wherein the Shock Remediation cycle having a chlorine dioxide CT Value ranges from 80 to 400 (mg/l×min). 
     
     
         17 . The system in accordance with  claim 16 , wherein the chlorine dioxide CT Value ranges from 90 to 350 (mg/l×min). 
     
     
         18 . The system in accordance with  claim 17 , wherein the chlorine dioxide CT Value ranges from 100 to 300 (mg/l/min). 
     
     
         19 . The system in accordance with  claim 1 , wherein controlling the Recovery Remediation cycle comprising:
 the process controller initiating the Recovery Remediation cycle;   measuring the chlorine dioxide concentration and calculating a chlorine dioxide Ct value;   sustaining the concentration of chlorine dioxide until the targeted chlorine dioxide Ct value is achieved;   and the process controller recordings   
       the time when the targeted chlorine dioxide Ct value is achieved and terminating the remediation cycle. 
     
     
         20 . The system in accordance with  claim 1 , wherein the Routine Remediation cycle further comprises a Daily Remediation cycle and/or Continuous 24/7 Remediation cycles. 
     
     
         21 . The system in accordance with  claim 20 , wherein the Routine Remediation cycle having a chlorine dioxide CT Value ranges from 80 to 400 (mg/l×min). 
     
     
         22 . The system in accordance with  claim 21 , wherein the chlorine dioxide CT Value ranges from 90 to 300 (mg/l×min). 
     
     
         23 . The system in accordance with  claim 22 , wherein the chlorine dioxide CT Value ranges from 100 to 250 (mg/l/min). 
     
     
         24 . The system in accordance with  claim 20 , wherein controlling the Daily Remediation cycles comprising:
 the process controller initiating the Daily Remediation cycle;   measuring the chlorine dioxide concentration;   calculating a chlorine dioxide Ct value;   sustaining the concentration of chlorine dioxide until the targeted chlorine dioxide Ct value is achieved;   and the process controller recording the time when the targeted chlorine dioxide Ct value is achieved and terminating the remediation cycle.   
     
     
         25 . The system in accordance with  claim 20 , wherein controlling the Continuous 24/7 Remediation cycles comprising:
 the process controller initiating the Continuous 24/7 Remediation cycles;   measuring the chlorine dioxide concentration;   calculating a chlorine dioxide Ct value;   sustaining the concentration of chlorine dioxide until the targeted chlorine dioxide Ct value is achieved,   and wherein the process controller records the time when the targeted chlorine dioxide Ct value is achieved terminating the remediation cycle, resets the chlorine dioxide Ct value to zero, then repeats the process.   
     
     
         26 . The system in accordance with  claim 1 , further comprising setting the chlorine dioxide chemical feed system(s) to their maximum output. 
     
     
         27 . The system in accordance with  claim 1 , further comprising controlling the sanitizer and pH control feed systems using time-based proportional control. 
     
     
         28 . The system in accordance with  claim 1 , further comprising sensors for measuring ORP, free chlorine, total chlorine, temperature and flow rate of the circulating water. 
     
     
         29 . The system in accordance with  claim 1 , wherein the chlorine dioxide feed system for control of chlorine dioxide comprises a chlorine dioxide generator. 
     
     
         30 . The system in accordance with  claim 1 , wherein the chlorine dioxide feed system comprises accelerated in-situ generation of chlorine dioxide. 
     
     
         31 . The system in accordance with  claim 1 , wherein the chlorine dioxide Ct value is calculated following the equation: 
       
         
           
             
               
                 Chlorine 
                 ⁢ 
                     
                 dioxide 
                 ⁢ 
                     
                 Ct 
                 ⁢ 
                     
                 value 
               
               = 
               
                 
                   [ 
                   
                     
                       ( 
                       
                         ∑ 
                            
                         
                           X 
                           n 
                         
                       
                       ) 
                     
                        
                     ÷ 
                        
                     n 
                   
                   ] 
                 
                    
                 × 
                    
                 T 
               
             
           
         
         Where: 
         “X n ” is the chlorine dioxide concentration in mg/l (or ppm) recorded at a point in time since beginning the remediation cycle. 
         “n” is the number of chlorine dioxide values recorded over a period of time since beginning the remediation cycle. 
         “T” is the period of time (minutes) that has lapsed since beginning the remediation cycle. 
       
     
     
         32 . The system in accordance with  claim 1 , wherein the chlorine dioxide Ct Value is calculated following the equation: 
       
         
           
             
               
                 Chlorine 
                 ⁢ 
                     
                 dioxide 
                 ⁢ 
                     
                 Ct 
                 ⁢ 
                     
                 value 
               
               = 
               
                 ∑ 
                     
                 
                   [ 
                   
                     
                       ( 
                       
                         ∑ 
                            
                         
                           
                             X 
                             n 
                           
                             
                           ÷ 
                              
                           n 
                         
                       
                         
                       ) 
                     
                        
                     × 
                        
                     T 
                   
                   ] 
                 
               
             
           
         
         Where: 
         “X n ” is the chlorine dioxide concentration in mg/l (or ppm) recorded at a point in time over the sampling period. 
         “n” is the number of chlorine dioxide values recorded over the sampling period. 
         “T” is the period of time (minutes) that has lapsed over the sampling period. 
       
     
     
         33 . A method for controlling multiple methods of remediation cycles for the treatment of water of an aquatic facility for immersion by humans, the method comprising:
 providing an integrated system comprising:
 a chlorine dioxide sensor in fluid communication with the water; 
 a chlorine dioxide feed system in fluid communication with the water, the chlorine dioxide feed system is downstream of the chlorine dioxide sensor, and chlorine dioxide is fed to the water during ON-Time; 
 a process controller in communication with the chlorine dioxide sensor and the chlorine dioxide feed system for measurement and control of chlorine dioxide in the water; 
 the process controller is programmed to control recovery remediation cycles and routine remediation cycles of the water, the recover remediation cycles having a different completion time interval and ClO 2  Setpoint than the routine remediation cycles, and completion of the recovery remediation cycles and the routine remediation cycles is determined by achieving a targeted chlorine dioxide CT Value; 
 the process controller is programmed to control the chlorine dioxide feed system using remedial time-based proportional control (remedial TBP), wherein the remedial TBP determines the chlorine dioxide feed system ON-Time following the formula: 
   
       
         
           
             
               
                 
                   [ 
                   
                     
                       
                         
                           ClO 
                           2 
                         
                         ⁢ 
                             
                         Setpoint 
                         ⁢ 
                             
                         
                           ( 
                           ppm 
                           ) 
                         
                       
                       - 
                       
                         Measured 
                         ⁢ 
                             
                         
                           ClO 
                           2 
                         
                         ⁢ 
                             
                         
                           ( 
                           ppm 
                           ) 
                         
                       
                     
                     
                       
                         ClO 
                         2 
                       
                       ⁢ 
                           
                       Dynamic 
                       × 
                       10 
                          
                       × 
                          
                       Dynamic 
                       ⁢ 
                           
                       Compensation 
                     
                   
                   ] 
                 
                    
                 × 
                    
                 Time 
                 ⁢ 
                     
                 Segment 
               
               = 
               
                 ON 
                 - 
                 Time 
               
             
           
         
         where,
 Time Segment is a segment of time reported in seconds or minutes; 
 ClO 2  Setpoint (ppm) is the ClO 2  Setpoint for the selected routine remediation cycle or recovery remediation cycle; 
 Measured ClO 2  (ppm) is the ClO 2  value measured by a chlorine dioxide sensor; 
 ClO 2  Dynamic is a concentration of ClO 2  being fed to the water from the chlorine dioxide feed system and is based on a total volume of water being treated per unit time (ClO 2  ppm/minute); and 
 Dynamic Compensation (DC) is a unique value for each aquatic facility and compensates effects of lag-time on measurement of the chlorine dioxide concentration in the water by the chlorine dioxide sensor after chlorine dioxide has been fed to the water from the chlorine dioxide feed system, and the DC has a value ranging from 0.2 to 2.0; 
 wherein, 
 the process controller initiating a remediation cycle; 
 the process controller feeding the chlorine dioxide from the chlorine dioxide feed system to the water during the On-Time; 
 measuring a chlorine dioxide concentration in the water using the chlorine dioxide sensor; and 
 the process controller stopping feeding of the chlorine dioxide from the chlorine dioxide feed system to the water when the targeted chlorine dioxide CT Value of the water is obtained. 
 
       
     
     
         34 . The method in accordance with  claim 33 , further comprising sensors for measuring ORP, free chlorine, total chlorine, temperature and flow rate of the circulating water. 
     
     
         35 . The method in accordance with  claim 33 , wherein chlorine dioxide feed system for control of chlorine dioxide comprises a chlorine dioxide generator. 
     
     
         36 . The method in accordance with  claim 33 , wherein chlorine dioxide feed system comprises accelerated in-situ generation of chlorine dioxide. 
     
     
         37 . The method in accordance with  claim 33 , wherein the Dynamic Compensation value is 1.0. 
     
     
         38 . The method in accordance with  claim 33 , further comprising optimizing the Dynamic Compensation following the formula: 
       
         
           
             
               
                 DC 
                 ⁢ 
                     
                 
                   ( 
                   
                     Optimized 
                     ⁢ 
                         
                     Value 
                   
                   ) 
                 
               
               = 
               
                 Theoretical 
                 ⁢ 
                     
                 
                   ClO 
                   2 
                 
                 ⁢ 
                     
                 
                   ( 
                   ppm 
                   ) 
                 
                 ⁢ 
                     
                 increase 
                 / 
                 Deviation 
                 ⁢ 
                     
                 from 
                 ⁢ 
                     
                 Setpoint 
                 ⁢ 
                     
                 
                   ( 
                   ppm 
                   ) 
                 
                    
                 × 
                    
                 Y 
               
             
           
         
       
       Where, 
       
         
           
             
               
                 “ 
                 
                   Theoretical 
                   ⁢ 
                       
                   
                     ClO 
                     2 
                   
                   ⁢ 
                       
                   
                     ( 
                     ppm 
                     ) 
                   
                   ⁢ 
                       
                   increase 
                 
                 ” 
               
               = 
               
                 
                   ( 
                   
                     ON 
                     - 
                     Time 
                     / 
                     Time 
                     ⁢ 
                         
                     segment 
                   
                   ) 
                 
                 × 
                 lag 
                 - 
                 time 
                    
                 × 
                    
                 
                   ClO 
                   2 
                 
               
             
           
         
         
           
             
               
                 “ 
                 
                   Deviation 
                   ⁢ 
                       
                   from 
                   ⁢ 
                       
                   Setpoint 
                 
                 ” 
               
               = 
               
                 
                   
                     ClO 
                     2 
                   
                   ⁢ 
                       
                   Setpoint 
                 
                    
                 - 
                    
                 
                   Measured 
                   ⁢ 
                       
                   
                     ClO 
                     2 
                   
                 
               
             
           
         
         “Y” is the “Lag-time Adjustment” having a value ranging from 1.01 to 2.0, preferably 1.05 to 1.8, and most preferred 1.1 to 1.5. 
       
     
     
         39 . The method in accordance with  claim 38 , wherein the Dynamic Compensation is automatically optimized by the process controller. 
     
     
         40 . The method in accordance with  claim 38 , wherein the Dynamic Compensation is optimized manually. 
     
     
         41 . The method in accordance with  claim 33 , wherein the Recovery Remediation cycle having a completion time interval ranging between 0.25 to 3.5 hours and a ClO 2  Setpoint ranging from 2 to 20 ppm. 
     
     
         42 . The method in accordance with  claim 41 , wherein the ClO 2  Setpoint ranges from 3 to 15 ppm. 
     
     
         43 . The method in accordance with  claim 42 , wherein the ClO 2  Setpoint ranges from 4 to 10 ppm. 
     
     
         44 . The method in accordance with  claim 33 , wherein the Routine Remediation cycle having a completion time interval ranging between 3.5 to 24 hours and a ClO 2  Setpoint ranging from 0.2 to 1.0 ppm. 
     
     
         45 . The method in accordance with  claim 44 , wherein the ClO 2  Setpoint ranges from 0.2 to 0.8 ppm. 
     
     
         46 . The method in accordance with  claim 45 , wherein the ClO 2  Setpoint ranges from 0.3 to 0.6 ppm. 
     
     
         47 . The method in accordance with  claim 33 , wherein the Recovery Remediation further comprises a Biofilm Remediation cycle and a Shock Remediation cycle. 
     
     
         48 . The method in accordance with  claim 47 , wherein the Bio-film Remediation cycle having a chlorine dioxide CT Value ranges from 300 to 3000 (mg/l×min). 
     
     
         49 . The method in accordance with  claim 48 , wherein the chlorine dioxide CT Value ranges from 400 to 2500 (mg/l×min). 
     
     
         50 . The method in accordance with  claim 49 , wherein the chlorine dioxide CT Value ranges from 500 to 2000 (mg/l/min). 
     
     
         51 . The method in accordance with  claim 47 , wherein the Shock Remediation cycle having a chlorine dioxide CT Value ranges from 80 to 400 (mg/l×min). 
     
     
         52 . The method in accordance with  claim 51 , wherein the chlorine dioxide CT Value ranges from 90 to 350 (mg/l×min). 
     
     
         53 . The method in accordance with  claim 52 , wherein the chlorine dioxide CT Value ranges from 100 to 300 (mg/l/min). 
     
     
         54 . The method in accordance with  claim 33 , wherein controlling the Recovery Remediation cycle comprising:
 the process controller initiating the Recovery Remediation cycle;   measuring the chlorine dioxide concentration and calculating a chlorine dioxide Ct value;   sustaining the concentration of chlorine dioxide until the targeted chlorine dioxide Ct value is achieved;   and the process controller recordings the time when the targeted chlorine dioxide Ct value is achieved and terminating the remediation cycle.   
     
     
         55 . The method in accordance with  claim 33 , wherein the Routine Remediation cycle further comprises a Daily Remediation cycle and/or Continuous 24/7 Remediation cycles. 
     
     
         56 . The method in accordance with  claim 55 , wherein the Routine Remediation cycle having a chlorine dioxide CT Value ranges from 80 to 400 (mg/l×min). 
     
     
         57 . The method in accordance with  claim 56 , wherein the chlorine dioxide CT Value ranges from 90 to 300 (mg/l×min). 
     
     
         58 . The method in accordance with  claim 57 , wherein the chlorine dioxide CT Value ranges from 100 to 250 (mg/l/min). 
     
     
         59 . The method in accordance with  claim 55 , wherein controlling the Daily Remediation cycles comprising:
 the process controller initiating the Daily Remediation cycle;   measuring the chlorine dioxide concentration;   calculating a chlorine dioxide Ct value;   sustaining the concentration of chlorine dioxide until the targeted chlorine dioxide Ct value is achieved;   and the process controller recording the time when the targeted chlorine dioxide Ct value is achieved and terminating the remediation cycle.   
     
     
         60 . The method in accordance with  claim 55 , wherein controlling the Continuous 24/7 Remediation cycles comprising:
 the process controller initiating the Continuous 24/7 Remediation cycles;   measuring the chlorine dioxide concentration;   calculating a chlorine dioxide Ct value;   sustaining the concentration of chlorine dioxide until the targeted chlorine dioxide Ct value is achieved,   and wherein the process controller records the time when the targeted chlorine dioxide Ct value is achieved terminating the remediation cycle, resets the chlorine dioxide Ct value to zero, then repeats the process.   
     
     
         61 . The method in accordance with  claim 33 , further comprising setting the chlorine dioxide chemical feed system(s) to their maximum output. 
     
     
         62 . The method in accordance with  claim 33 , further comprising controlling the sanitizer and pH control feed systems using time-based proportional control. 
     
     
         63 . The method in accordance with  claim 33 , wherein the chlorine dioxide Ct value is calculated following the equation: 
       
         
           
             
               
                 Chlorine 
                 ⁢ 
                     
                 dioxide 
                 ⁢ 
                 
                     
                      
                 
                 ⁢ 
                 Ct 
                 ⁢ 
                     
                 value 
               
               = 
               
                 
                   [ 
                   
                     
                       ( 
                       
                         ∑ 
                         
                           X 
                           n 
                         
                       
                       ) 
                     
                     ÷ 
                     n 
                   
                   ] 
                 
                 × 
                 T 
               
             
           
         
         Where: 
         “X n ” is the chlorine dioxide concentration in mg/l (or ppm) recorded at a point in time since beginning the remediation cycle. 
         “n” is the number of chlorine dioxide values recorded over a period of time since beginning the remediation cycle. 
         “T” is the period of time (minutes) that has lapsed since beginning the remediation cycle. 
       
     
     
         64 . The method in accordance with  claim 33 , wherein the chlorine dioxide Ct Value is calculated following the equation: 
       
         
           
             
               
                 Chlorine 
                 ⁢ 
                     
                 dioxide 
                 ⁢ 
                 
                     
                      
                 
                 ⁢ 
                 Ct 
                 ⁢ 
                     
                 value 
               
               = 
               
                 ∑ 
                 
                   [ 
                   
                     
                       ( 
                       
                         ∑ 
                         
                           
                             X 
                             n 
                           
                           ÷ 
                           n 
                         
                       
                       ) 
                     
                     × 
                     T 
                   
                   ] 
                 
               
             
           
         
         Where: 
         “X” is the chlorine dioxide concentration in mg/l (or ppm) recorded at a point in time over the sampling period. 
         “n” is the number of chlorine dioxide values recorded over the sampling period. 
         “T” is the period of time (minutes) that has lapsed over the sampling period. 
       
     
     
         65 . The method in accordance with  claim 33 , further comprising UV activation of chlorite ions to produce chlorine dioxide. 
     
     
         66 . The method in accordance with  claim 33 , further comprising the cyclic process wherein hypobromous acid activates chlorite to produce chlorine dioxide.

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